The present invention relates to a special process for printing hydrophobic fibre materials with disperse dyes by the resist printing process.
The resist printing process with disperse dyes is known for hydrophobic fibre materials. However, these materials, especially polyester fibre materials, are usually printed by the so-called discharge resist process in which the predyed or preprinted base dye is destroyed locally by treatment with a strongly alkaline assistant and by printing these areas with one or several other dyes which must by discharge resistant. Treatment with the discharge agent is, however, ecologically and economically disadvantageous; thus, for example, the treated fibre material may be attacked and damaged by the action of strong alkali. There is therefore a need for a simpler resist printing process, which is gentle on the fibre, for printing hydrophobic fibre materials, especially polyester fibre materials.
Surprisingly, it has now been found that the hydrophobic fibre material can be printed in a manner which is gentle on the fibre by the process of this invention, the resulting print having good allround fastness properties and, in particular, very good fastness to hot light.
Accordingly, this application relates to a process for printing hydrophobic fibre materials with disperse dyes, which process comprises
1) dyeing or printing the fibre materials overall with a disperse dye, and
2) printing the fibre materials in areas with a printing paste, which comprises
as component (A), at least one cationic assistant,
as component (B), at least one polyethylene glycol,
as component (C), at least one nonionogenic detergent
and, optionally,
as component (D), at least one disperse dye,
it being possible for steps 1) and 2) to be carried out in any sequence and for step 2) to be carried out repeatedly without using any dye, or using different dyes, and, if necessary, drying the fibre material thus treated and then fixing the dye on the fibre material by heat treatment.
Disperse dyes suitable for steps 1) and 2) of the novel process are, for example, those dyes which are described in Colour Index, 3rd edition (3rd Revision 1987 including additions and amendments up to No. 85) under xe2x80x9cDisperse Dyesxe2x80x9d. These dyes include, for example, car-boxylic acid- and/or sulfonic acid group-free nitro, amino, aminoketone, ketoninime, methine, polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine or coumarine dyes and, in particular, anthraquinone and azo dyes, such as mono- or disazo dyes.
Dyes which are preferably used for the novel process are those of formulae 
wherein
R1 is hydroxy or amino,
R2 is hydrogen; phenyl which is unsubstituted or substituted by C1-C4 alkyl, C1-C4 alkoxy, hydroxy-C1-C4 alkyl or C1-C4 sulfo,
R3 is hydrogen, hydroxy, amino or nitro,
R4 is hydrogen, hydroxy, amino or nitro,
R5 is hydrogen, halogen or C1-C4 alkoxy, and
R6 is hydrogen, halogen or xe2x80x94Oxe2x80x94(CH2)2xe2x80x94Oxe2x80x94COOR7, wherein R7 is C1-C4 alkyl or phenyl, 
xe2x80x83wherein
R8 and R9 are each independently of the other hydrogen, xe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94OX or xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2)4xe2x80x94OX, wherein X is hydrogen or xe2x80x94COCH3, 
xe2x80x83wherein
Rio is amino which is mono- or disubstituted by xe2x80x94(CH2)2xe2x80x94Oxe2x80x94COCH3, xe2x80x94(CH2)2xe2x80x94CN, xe2x80x94CH(CH3)xe2x80x94COOCH3 or xe2x80x94CH2xe2x80x94C(OH)CH3,
R11 is hydrogen, C1-C4 alkyl or halogen,
R12 is hydrogen or NHCOR15, wherein R15 is C1-C3alkyl,
R13 is hydrogen or halogen, and
R14 is halogen, nitro or cyano, 
wherein R16 is methyl, ethyl or xe2x80x94(CH2)2xe2x80x94Oxe2x80x94C1-C2 alkyl, and 
The amounts in which the disperse dyes are used in the dye baths or printing pastes can vary, depending on the desired tinctorial strength; advantageous amounts having been found to be usually from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, based on the total sum of the dyes per 1 litre of the liquor, or from 0.01 to 400 g, preferably from 0.2 to 300 g, more preferably from 0.5 to 200 g, of the dyes per kg of printing paste.
If the hydrophobic fibre material is dyed in step 1), a continuous dyeing process is usually used, for example the padding process. If appropriate, the dyed material is dried before further treatment, for example for 1 to 5 minutes at 80 to 1 40xc2x0 C.
In addition to the dye, the dye liquor can contain other customary additives, for example acid donors, such as aliphatic amine chlorides or magnesium chloride, the aqueous solutions of inorganic salts, such as of alkali chlorides or alkali sulfates, alkali hydroxides, urea, thickeners, such as alginate thickeners, water-soluble cellulose alkyl ether, and also levelling agents, antifoams and/or deaerators, penetration accelerators, migration inhibitors, UV ab-sorters and wetting agents.
The printing paste which may optionally be used in step 1) is a printing paste customarily used in printing technology, which comprises, in addition to the dye, the conventional assistants, for example thickeners of natural or synthetic origin, for example commercially available alginate thickeners, starch ethers or carob seed grain ether, in particular sodium alginate, by themselves or in admixture with modified cellulose, preferably with 20 to 25% by weight of carboxymethylcellulose.
In the above printing paste, it is preferred to use synthetic thickeners, for example those based on poly(meth)acrylic acids, poly(meth)acrylamides, and their co- or terpolymers. If desired, the printing paste can also contain acid donors, such as butyrolactone or sodium hydrogenphosphate, preservatives, sequestrants, emulsifiers, water-insoluble solvents, oxidants, UV absorbers or deaerators.
The material printed in step 1) may optionally be dried before further treatment, for example for 1 to 5 minutes at 80 to 140xc2x0 C.
Suitable components (A) in the printing paste used in step 2) are in particular organic poly-mer compounds containing quaternised amines; salts of nitrogen-containing organic polymer compounds, or aminoxides of formula 
wherein
R is an aliphatic radical containing 8 to 24 carbon atoms, and
R1 and R2 are each independently of the other an aliphatic radical which is unsubstituted or substituted by hydroxy, C1-C4 alkoxy, halogen, sulfo or acyl containing 1 to 24 carbon atoms, or a radical xe2x80x94(CH2CH2O)kW, wherein k is a number from 2 to 80, and W is C1-C4alkyl, acyl, phenyl, naphthyl, benzyl or, preferably, hydrogen.
R defined as aliphatic radical containing 8 to 24 carbon atoms is, for example, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl. R1 and R2 defined as aliphatic radical containing 1 to 24 carbon atoms is, for example, a C1-C24 alkyl radical, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl.
Of these compounds, the organic polymer compounds based on the polymono- and polydi-allylamines merit particular mention, for example polydiallyl ammonium hydrochloride or polydiallyldimethyl ammonium chloride, and also ethoxylated and/or propoxylated fatty amines which are quaternised, for example, with methyl chloride, dimethyl sulfate or benzyl chloride, such as dodecylamine which is reacted with 17 ethylene oxide units and quater-nised with methyl chloride.
The printing paste contains 1 to 70, preferably 1 to 40, more preferably 1 to 30 g of the catio-nic assistant per 1 kg of the printing paste.
A suitable component (B) for use in the printing paste used in step 2) is advantageously a polyethylene glycol having a molecular weight in the range from 200 to 9000, preferably from 200 to 2500.
The printing paste usually comprises 5 to 140, preferably 5 to 60 g, of a polyethylene glycol per 1 kg of printing paste.
Component (C) in the printing paste used in step 2) is, for example, fatty acid polyglycol esters which are optionally end-capped, fatty acid esters of polyvalent alcohols, for example diethylene glycol or glycerol, naturally occurring and optionally partially saponified neutral fats or, preferably, those compounds which are obtained by adding 4 to 80 ethylene oxide units and/or propylene oxide units to fatty alcohols, fatty amines, fatty acids or alkylaryls, such as nonyl- or octylphenol.
Examples of these compounds to be mentioned are cetyl alcohol containing 4-6 ethylene oxide units, cetyl alcohol containing 10-14 ethylene oxide units, tallow fatty alcohol containing 10 to 30 ethylene oxide units, lauryl alcohol containing 5-8 ethylene oxide units, nonyl-phenol containing 3 to 15 ethylene oxide units, castor oil containing 30-50 ethylene oxide units or oleic acid containing 5 to 20 ethylene oxide units.
It is advantageous to use nonionogenic detergents in the printing paste used according to this invention, which detergents do not foam or foam only little.
The printing paste usually contains 1 to 70, preferably 5 to 40 g, of the nonionogenic detergent per 1 kg of printing paste.
The printing paste used in step 2) advantageously contains as additional component a poly-propylene glycol having a molecular weight in the range from 100 to 2000, preferably from 200 to 600, or a dipropylene glycol.
In addition to the components mentioned above, the printing paste used in step 2) can also contain other conventional assistants, for example usefully thickeners of natural or synthetic origin, such as commercially available alginate thickeners, starch ethers or carob seed grain ether, in particular sodium alginate, by themselves or in admixture with modified cellulose, in particular containing preferably 20 to 25% by weight of carboxymethylcellulose. It is also possible to use synthetic thickeners in the printing paste of this invention, for example those based on poly(meth)acrylic acids, poly(meth)acrylamides, and their co- or terpolymers.
The printing paste used in step 2) can also contain alkylene oxide condensates (block polymers), such as ethylene oxide adducts with polypropylene oxide (so-called EO-PO block polymers) and propylene oxide adducts with polyethylene oxide (so-called reverse EO-PO block polymers). It is particularly preferred to use ethylene oxide/propylene oxide block polymers, the polypropylene oxide base of which has a molecular weight in the range from 1000 to 8000, preferably from 1000 to 5000, more preferably from 2000 to 4000, and an ethylene oxide contained in the entire molecule of 10 to 90%, preferably of 20 to 80%.
If desired, the printing paste used in step 2) can also contain acid donors, such as butyrolac-tone or sodium hydrogenphosphate, preservatives, sequestrants, emulsifiers, water-inso-luble solvents, oxidants, UV absorbers or deaerators.
Suitable preservatives are, in particular, formaldehyde-donating agents, such as paraformal-dehyde and trioxane, especially aqueous, about 30 to 40% by weight formaldehyde solutions; as UV absorbers in particular triazine UV absorbers; as sequestrants e.g. nitrilotriace-tic sodium, ethylenediaminetetracetic sodium, preferably sodium polymetaphosphate, more preferably sodium hexametaphosphate; as emulsifiers preferably adducts of an alkylene oxide and a fatty alcohol, preferably an adduct of oleyl alcohol and ethylene oxide; as water-insoluble solvent high-boiling saturated hydrocarbons, especially paraffins having a boiling range from about 160 to 210xc2x0 C. (so-called white spirits); as oxidants e.g. an aromatic nitro compound, preferably an aromatic mono- or dinitrocarboxylic acid or -sulfonic acid which may be in the form of an alkylene oxide adduct, in particular a nitrobenzenesulfonic acid, and as deaerator e.g. high-boiling solvents, preferably turpentine oils, higher alcohols, preferably C8-to C10 alcohols or terpene alcohols.
The novel process can be used for different hydrophobic fibre materials.
Polyester fibre materials are preferred. Suitable polyester fibre materials are those which consist entirely or partly of polyester. Examples thereof are cellulose ester fibres, for example cellulose-2xc2xd-acetate fibres and -triacetate fibres and, in particular, linear polyester fibres which may also be acid-modified and which are obtained, for example, by condensing tere-phthalic acid with ethylene glycol, or isophthalic acid or terephthalic acid with 1,4-bis(hydro-xymethyl)cyclohexane, and also fibres of mixed polymers of terephthalic and isophthalic acid with ethylene glycol. Also suitable are polyester-containing fibre blends, i.e. mixtures of poly-ester and other fibres, in particular cotton/polyester fibre materials. Wovens, knits or webs of these fibres are mainly used.
For printing the hydrophobic fibre materials, the printing paste is applied overall or in areas directly onto the fibre material, conveniently using printing machines of conventional make, for example rotogravure, rotary screen printing and flat screen printing apparatus.
The novel process is preferably carried out in a xe2x80x9cone step processxe2x80x9d on the xe2x80x9cH. W. Dyeing and Discharge Printing Linexe2x80x9d apparatus, of Johannes Zimmer, A-9020 Klagenfurt (WO 96/28604).
If required, the fibre material is dried after steps 1) and 2) have been carried out, for example at temperatures of up to 150xc2x0 C., preferably in the range from 80xc2x0 to 140xc2x0 C. Drying can also be carried out by IR irradiation.
The subsequent fixing of the fibre material is usually carried out by thermofixation or super-heated steam under atmospheric pressure (HT fixing). Fixing is carried out in this case under the following conditions:
HT fixing: 1 to 50 minutes at 100 to 240xc2x0 C., preferably 1 to 12 minutes at 160 to 200xc2x0 C., thermofixing: 1 to 50 minutes at 100 to 240xc2x0 C., preferably 1 to 10 minutes at 160 to 220xc2x0 C.
The fibre material dyed and/or printed according to this invention is normally washed off after fixing and is then finished in conventional manner by cleaning in alkaline medium under reductive conditions, e.g. using sodium dithionite. After cleaning, the fibre material is rinsed again and dried.
The prints obtainable by the novel process on polyester fibre materials have good allround fastness properties; they have, for example high fibre-dye bond stability both in the acid and in the alkaline range, good fastness to wet treatment, such as fastness to washing, water, seawater and perspiration, good fastness to chlorine, fastness to rubbing, ironing and pleating and are particularly distinguished by an extension of the brilliant shades with high fastness to light and hot light.
This invention also relates to a printing paste formulation, which comprises,
as component (A), 1 to 50% by weight of a cationic assistant,
as component (B), 1 to 50% by weight of a polyethylene glycol, and
as component (C), 1 to 50% by weight of a nonionogenic detergent.
The novel formulation is distinguished by excellent storage stability. There is no phase separation even after storing for 2 months at temperatures from xe2x88x9210 to +40xc2x0 C.
Components (A), (B) and (C) have the above meanings and preferred meanings.
A preferred printing paste formulation is that which comprises,
as component (A), 2 to 20% by weight of a cationic assistant,
as component (B), 5 to 50% by weight of a polyethylene glycol, and
as component (C), 3 to 30% by weight of a nonionogenic detergent.
Besides the components (A), (B) and (C), the novel printing paste formulation can contain as additional component a polypropylene glycol having a molecular weight from 100 to 2000, preferably from 200 to 600, or a dipropylene glycol and/or at least one disperse dye.
The following Examples illustrate the invention in more detail. Temperatures are given in degrees Celsius and parts and percentages are by weight, unless otherwise stated. The relationship between parts by weight to parts by volume is the same as that between the kilo-gramme and the litre.